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Workpackage: Liquid biofuels

Michael Studer, BFH; Jeremy Luterbacher, EPFL

Towards diesel and jet-fuel production from lignocellulosic biomass through biological and chemical processing

11.09.16 1 [email protected]


Subsequent biochemical and catalytic conversion of lignocellulosic biomass to diesel and jet-fuel

[email protected] 11.09.16 2

Ligno-‐cellulosic feedstock

Conversion to carboxylic acids

Conversion to alkanes and α-

olefins

Market

Cataly(c conversion

Biochemical conversion


Biochemical conversion

3 [email protected] 11.09.16


Bioprocessing of beech wood to lactic acid


Product

(Steam) pretreatment

Solids washing

Cellulose hydrolyse

Liquid detoxification

Pentose fermentation

(Intermediate) product separation

Hexose fermentation

Enzym production

Ligno-cellulose

Solid/liquid separation

Product

(Steam) pretreatment

Consolidated bioprocessing

(Intermediate) product separation

Ligno-cellulose

•  Loosens-‐up cellulose lignin entanglement •  Releases C5 sugars

Enzymes break solid cellulose down into glucose monomers

C5 and C6 sugars are fermented to desired product

1)   Adapted from: A. Aden et al. 2002, Lignocellulosic Biomass to Ethanol Process Design and Economics U7lizing Co-‐Current Dilute Acid Prehydrolysis and Enzyma7c Hydrolysis for Corn Stover, NREL, Golden CO


Steam pretreatment – Commercial relevance

Advantages[1,2]: §   No chemicals §   Particle size reduction by explosion §   Simplified downstream processing

§   Moderate energy requirements; Low Capex §   11 out of 14 commercial plants (cellulosic) use steam-ex


[1] E Tomás-‐Pejó, M Ballesteros, MJ Negro, Bioresour Technol, 2010. [2] S Brethauer, M Studer, Chimia, 2015. [3] Biochemtex Biorefinery, Crescen(no, Italy.

[3]

[3]

[1] E Tomás-‐Pejó, M Ballesteros, MJ Negro, Bioresour Technol, 2010. [2] S Brethauer, M Studer, Chimia, 2015. [3] Biochemtex Biorefinery, Crescen(no, Italy.


Two-stage steam pretreatment

[email protected] 11.09.16 6 [1] Balan, R. et al. , 36th Symposium on Biotechnology for Fuels and Chemicals, Bal(more USA, 2016

first stage (high xylan yield)

liquid separa(on

second stage (high glucan yield)


Consolidated bioprocessing of carboxylic acids



Consolidated bioprocessing of pretreated beech to lactic acid


O2

oxygen conc.

y-positionCe

llulo

lytic

en

zym

es

Released sugar

Lact

ic

acid

pretreated biomass slurry

fungal biofilm(aerobic)

yeast/bacterial biofilm (anaerobic)

dense membrane

[1] Brethauer, S. and Studer, M. Energy Environ. Sci., 2014, 7 1446

§   Integration of

§   Cellulase production §   Hydrolysis §   Fermentation


Lactic acid production from pure cellulose

§   Trichoderma reesei as celluloytic enzyme producer

§   Lactobacillus pentosus as lactic acid forming microorganism


40

30

20

10

0

lact

ic a

cid

conc

. /gL

-1

216192168144120967248240

time /h

Cellulose concentration: 17.5g/L 35g/L 50g/L

0.64 g/g

0.58 g/g

0.54 g/g


Lactic acid production from pretreated beech wood

§   Beech wood

§   Pretreatment §   1-stage §   230°C, 15Min §   Explosive discharge §   Washed §   53% w/w cellulose




20

15

10

5

0

lact

ic a

cid

conc

. /gL

-1

144120967248240

time /h

Solids loading: 1.9% 2.2% 3.9%

0.73 g/g

0.87 g/g

0.83 g/g


Co-fermentation of cellulose and xylose to lactic acid

§   L. pentosus facultative heterofermentative microorganism



Co-fermentation of 2-stage pretreated beech with continuous feed of hydrolyzate


§   Beech wood §   2-stage pretreatment

§   Stage 1: 180°C, §   Stage 2: 230°C, 15Min §   Explosive discharge

§   2.2% w/w solids loading §   Continuous feeding of

hydrolyzate §   Over 100h



10

8

6

4

2

0

conc

entra

tion

/gL-1

216192168144120967248240

time /h

lactic acid acetic acid ethanol xylose


Catalytic upgrading Tandem hydrogenation/dehydration of carboxylic acids to α-olefins



Catalytic upgrading of lactic acid to transportation fuels

§   Requirements for α-olefin production: §   Aqueous phase §   Linear §   No double bond migration


C9+ transportation fuels

Oligomerization1

Amberlyst 70

1Bond et al. Science. 2010


Tandem hydrogenation/dehydration

§   5% Cu/SiO2-Al2O3 (70% SiO2)

§   Flow reactor

§   Conditions: §   1.2% lactic acid in water §   240 & 270°C §   H2 atmosphere §   Flow rates of 10 and 100ml/Min



Challenges


Side reactions

overhydrogenation

esterification Isomerization

double bond migration

structural rearrangement


Catalytic upgrading of lactic acid in aqueous solvent


Aqueous feed: lower dehydra(on ac(vity


Catalytic upgrading Condensation reactions of carboxylic acids to aromatics

18


Condensation reactions of carboxylic acids

19

Ketonization:

Advantage: high selectivity Disadvantage: single condensation possible

Aldol condensation:

Advantage: multiple condensation possible no carbon loss (deoxygenation without hydrogen)


Catalytic upgrading of acetic acid



Reaction conditions

•   Catalyst 2% Cu/ZrO2

•   Similar low dispersion ~5%

•   ZrO2 prepared by precipitation method

•   Deposition of Cu by impregnation

•   Conditions 400 °C

•   10 bar H2 pressure

•   Flow 0.01 ml/min

•   Gas flow 20 ml/min



Products


olefins

Aroma(c hydrocarbons

water

H2O


Carbon balance – total carbon


0

5

10

15

20

25

C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17

C mol (%

)

Carbon number

Carbon balance

liquid hydrocarbons gas olefins oxygenates 69.6

25.9

4.5 0

20

40

60

80

organic gas water

C mol (%

)

phase

Carbon balance

carbon distribu(on


Cross ketonization

14


Summary

§   SCCER enabled cross discipline project

§   Two-stage steam pretreatment was developed

§   Consolidated bioprocessing of wood to lactic acid §   Up-scaled the process to 3L

§   Tandem hydrogenation/dehydration of lactic acid to α-olefins in aqueous phase

§   Aldol condensation of aceton derived from acetic acid yields jet-fuel components



Acknowledgement

11.09.16 29

-   Robert Balan

-   Robert Shahab

-   Charilaos Xiros

-   Jher Hau Yeap

-   Bartosz Rozmyslowicz

[email protected]


Biochemical production of carboxylic acids from lignocellulosic biomass

§   Corn stover, mixed grasses, beech wood chips

§   Lactic acid, butyric acid, mixed C2 to C6 carboxylic acids

§   Optimized mixture of carboxylic acids for catalytic conversion to alkanes and olefins

§   Simple, robust, highly integrated process



Catalytic upgrading of lactic acid to transportation fuels

§   Requirements for α-olefin production: §   Aqueous phase §   Linear §   No double bond migration


C9+ transportation fuels

Oligomerization1

Amberlyst 70

1Bond et al. Science. 2010


0

5

10

15

20

25


C mol (%

)

Carbon number

Carbon balance

hydrocarbons oxygentates 1

0.33

0.02 0

0.2

0.4

0.6

0.8

1

1.2

ace(c acid acetone oil

O/C ra

(o

O/C ra(o

10

Carbon balance – organic phase


Carbon balance – gas phase

11

0

5

10

15

20

25


C mol (%

)

Carbon number

Carbon balance

gas olefins acetone


Carbon balance – water phase

0

5

10

15

20

25


C mol (%

)

Carbon number

Carbon balance

acetone

12


78 80 82 84 86 88 90 92

0 2 4 6 8 10 12

Conversion

of a

cetone

(mol %)

Time (days)

Conversion Regenera(on

Conversion of acetone

-‐10 -‐9 -‐8 -‐7 -‐6 -‐5 -‐4 -‐3 -‐2 -‐1 0

0 1 2 3 4 5 6 7 8

carbon

mol (%

)

Time (days)

conversion decrease propylene yield decrease

13


Acknowledgement

11.09.16 36 [email protected]

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